The photoionization enegies and electronic structure of the valence band (VB) of SbSI crystal can be calculated by solving the Hartree-Fock-Roothan matrix equation FC=SCε where the diagonal matrix ε gives the electron state energies. These energies experimentally are studied in a wide temperature range by PHI 5700/660 Physical Electronics Spectrometer using excitation source Al Ka monochromatic radiation (1486.6 eV). The photoelectron spectra were measured in the energy range 0 - 1450 eV.